This review summarizes recent advances and highlights the structure–property relationship on metal–organic framework-based materials for carbon dioxide capture and conversion.

This review summarizes recent advances in the design and synthesis of stable MOFs and highlights the relationships between the stability and functional applications.

The rational integration of multiple functional components into a composite material could result in enhanced activity tailored for specific applications. Herein, imidazolium-based poly(ionic liquid)s (denoted as polyILs) have been confined into the metal−organic framework (MOF) material MIL-101 via in situ polymerization of encapsulated monomers. The resultant composite polyILs@MIL-101 exhibits good CO 2 capture capability that is beneficial for the catalysis of the cycloaddition of CO 2 with epoxides to form cyclic carbonates at subatmospheric pressure in the absence of any cocatalyst. The significantly enhanced activity of polyILs@MIL-101, compared to either MIL-101 or polyILs, is attributed to the synergistic effect among the good CO 2 enrichment capacity, the Lewis acid sites in the MOF, as well as the Lewis base sites in the polyILs.

Metal–organic frameworks (MOFs) have demonstrated great potentials toward catalysis, particularly in the establishment of structure–property relationships. Herein, an unusual OOP (out-of-plane) porphyrin-based MOF, synthesized by controlling the metal ion release with an unprecedented In­(OH)3 precursor, possesses high stability and exhibits unexpectedly high photocatalytic hydrogen production activity, far surpassing the isostructural in-plane porphyrin-based MOF counterparts. In the MOF structure, indium ions not only form indium–oxo chains but also metalate the porphyrin rings in situ, locating above the porphyrin plane instead of fitting in a coplanar fashion into the cavity and affording an unusual OOP porphyrin. Control experiments demonstrate that the OOP In­(III) ions readily detach from the porphyrin rings under light excitation, avoiding the fast back electron transfer and thus greatly improving electron–hole separation efficiency and photocatalytic performance. To our knowledge, this is an unprecedented report on boosting MOF photocatalysis on the basis of special metalloporphyrin behavior.

An In-based metal-organic framework, with 1D nanotubular open channels, In2(OH)(btc)(Hbtc)0.4(L)0.6·3H2O (1), has been synthesized via an in situ ligand reaction, in which 1,2,4-H3btc is partially transformed into the L ligand. Compound 1 exhibits exceptional thermal and chemical stability, especially in water or acidic media. The activated 1 presents highly selective sorption of carbon dioxide (CO2) over dinitrogen. Interestingly, diffuse-reflectance infrared Fourier transform spectroscopy with a carbon monoxide probe molecule demonstrates that both Lewis and Brønsted acid sites are involved in compound 1. As a result, as a heterogeneous Lewis and Brønsted acid bifunctional catalyst, 1 possesses excellent activity and recyclability for chemical fixation of CO2 coupling with epoxides into cyclic carbonates under mild conditions. In addition, the mechanism for the CO2 cycloaddition reaction has also been discussed.